Novel catalysts and process for liquid hydrocarbon fuel production

ABSTRACT

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from U.S. Provisional PatentApplication Ser. No. 61/273,856 filed Aug. 10, 2009. The entirety ofthat provisional application is incorporated herein by reference.

STATEMENT OF GOVERNMENT SUPPORT

This invention was made with government support under Contract No.DE-FG3606GO86025 awarded by the U.S. Department of Energy. Thegovernment may have certain rights in the invention.

FIELD OF THE INVENTION

This invention relates to the field of syngas conversion and morespecifically to the field of converting synthesis gas to high qualityhydrocarbon mixtures and includes the novel catalysts involved in suchconversion.

BACKGROUND OF THE INVENTION

The Fischer-Tropsch process involves a catalyzed chemical reactionwhereby synthesis gas, which is a mixture of carbon monoxide andhydrogen, is converted into liquid hydrocarbons. The most commoncatalysts generally used in the process are based on iron, cobalt,nickel, and ruthenium. The catalysts generally contain, in addition tothe active metal, a number of promoters as well as high surface areabinders/supporters such as silica, alumina, or zeolites. This process,which has been in commercial use for many years, produces higherhydrocarbon materials in the form of synthetic petroleum substitutesfrom coal, natural gas, heavier oil, or solid biomass for use assynthetic lubrication oil or synthetic fuel. The process involvesmultiple competing chemical reactions that subsequently result in bothdesirable products and undesirable byproducts.

Numerous patents exist that involve the Fischer-Tropsch synthesisprocess and catalysts used in such syntheses. However, the presentinvention discloses a novel process utilizing novel catalysts to producehigh quality liquid hydrocarbons in only one step, thereby eliminatingthe necessity for typical further processing and effectively eliminatingone or more processing steps or reactors and producing high qualityhydrocarbon products via only one reactor.

The present invention discloses a novel process and system in whichsyngas is converted into high quality gasoline components, aromaticcompounds, and lower molecular olefins in one reactor. Moreover, theprocess utilizes a novel molybdenum-zeolite catalyst in high pressurehydrogen for conversion. Additionally, the process also utilizes a novelrhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst inhigh pressure hydrogen for conversion.

SUMMARY OF THE INVENTION

The present invention provides for novel catalysts and a novel processand system for utilizing these catalysts for converting low H₂/CO molarratio synthesis gas to hydrocarbon mixtures composed of high qualitygasoline, low molecular weight gaseous olefins, and/orbenzene/naphthalene-derived aromatic compounds. The composition of theliquid hydrocarbon phase can be adjusted to show >90% aromatics (e.g.,benzene, toluene, and para-xylene) using HZSM-5 as the acid function;whereas, the H-Y-faujasite acid catalyst produces a liquid having acomposition of >90% iso-paraffins and cyclo-paraffins. The invention isdistinct and different from existing prior art and processes in manyrespects including, but not limited to: the catalysts use molybdenum(Mo) or rhenium (Re) as the main active components for the reaction; thecatalysts use a zeolite (HZSM-5, Y, Mordenite, MCM-22, MCM-41,H-Y-faujasite, H-beta, and the like) as the supporting material; theactive phase of the catalysts is composed of carburized/reducedMo-species (Re) or a non-zeolite, such as silica-alumina,heteropolyacid; the reaction proceeds mainly inside cages of the zeolitesupport, which effectively inhibits the formation of heavierlinear-chain hydrocarbons (>C₇); and the catalysts produce alcohols(methanol, ethanol, and propanol) as the primary intermediate productsfor hydrocarbon formation which results from the dehydration of thesealcohols. Moreover, the process of the present invention effectivelyremoves one or more reactors in the process of producing high qualitygasoline hydrocarbon products and produces such products from syngas inone step.

This invention demonstrates how a mixture of carbon monoxide andhydrogen (synthesis gas) can be converted into various hydrocarbonproducts. The origin of the synthesis gas may be from biorenewablesources such as biomass, grass, woody biomass, wastewater treatmentsludges, industrial and municipal, and any type of lignocelluloses. Inaddition, the source of the synthesis gas can be derived from petroleumsources such as natural gas, light hydrocarbons, liquid hydrocarbons, orpetroleum coke. Finally, the synthesis gas can be developed from a hostof alternative sources of carbon such as coal, lignite, tar sands, shaleoils, coal bed methane, and the hydrocarbon “ices” such as methanehydrate, and mixtures of light gas hydrates.

With the foregoing and other objects, features, and advantages of thepresent invention that will become apparent hereinafter, the nature ofthe invention may be more clearly understood by reference to thefollowing detailed description of the preferred embodiments of theinvention and to the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

These drawings accompany the detailed description of the invention andare intended to illustrate further the invention and its advantages:

FIG. 1 is a graphical illustration of the overall process of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention discloses a process and system for the conversionof a mixture of carbon monoxide and hydrogen (synthesis gas) intovarious hydrocarbon products. The origin of the synthesis gas may befrom biorenewable sources including, but not limited to, biomass, grass,woody biomass, wastewater treatment sludges, industrial and municipal,and any type of lignocelluloses. In addition, the source of thesynthesis gas can be derived from petroleum sources such as natural gas,light hydrocarbons, liquid hydrocarbons, or petroleum coke. Finally, thesynthesis gas can be developed from a host of alternative sources ofcarbon such as coal, lignite, tar sands, shale oils, coal bed methane,and the hydrocarbon “ices” such as methane hydrate, and mixtures oflight gas hydrates.

The present invention comprises solid catalysts for the selectiveconversion of a gas mixture containing carbon monoxide and hydrogen asthe major components into liquid hydrocarbons. One novel element of thistechnology is the use of a bi-functional catalyst: (1) showing a metalcomponent that converts the CO and H₂ into alcohols; and (2) showing anacid component that converts the alcohols into olefins, alkanes,branched alkanes, cyclic alkanes, and aromatics. The choice of acatalyst that produces alcohol intermediates circumvents the problems ofa broad molecular weight distribution of the products that plagues othersynthesis gas conversion catalysts and techniques which employCO-insertion chemistry as the chain growth mechanism. When the metalcomponent is chosen to produce a mixture of higher-molecular-weightalcohols, such as ethanol, propanol, etc. and oxygenates, the chemicalequilibrium reactions do not limit the conversion of synthesis gas ashas been observed when the intermediate product is only methanol.

The synthesis gas conversion into higher-molecular-weight alcohols ofthe present invention was achieved using a transition metal that wasactive as either the oxide or the sulfide. This last considerationallows the use of the catalyst in feed streams that showsulfur-containing compounds in low concentrations as might beencountered in synthesis gas obtained from gasification of coals andpetroleum coke products. Such a sulfur-tolerant catalyst precludes theneed for desulfurization of the raw synthesis gas stream.

An additional consideration for the choice of the metal syngasconversion catalyst component is the desirability for producing highermolecular weight alcohols. It has been shown that the reaction rate toform gasoline liquids over H-ZSM-5 was 8-10 times higher when thesubstrate was butanol rather than methanol. Amit C. Gujar, VamshiKrishna Guda, Michael Nolan, Qiangu Yan, Hossein Toghiani, and Mark G.White, “Reactions of Methanol and Higher Alcohols over H-ZSM-5”, AppliedCatalysis, A. General 363 (2009) 115-121. Thus, a metal synthesis gasconversion catalyst that produces higher-molecular-weight-alcoholintermediates is highly desirable over a metal catalyst that makes onlymethanol as an intermediate.

An essential part of the novel design of the present invention is theuse of metal-containing, acidic solids that show a pore structure whichdetermines the types of hydrocarbon products obtained under reactionconditions. That is, the reaction products obtained over a medium-porezeolite such as H-ZSM-5 show a high preference for aromatic hydrocarbons(>80%) over alkanes and alkenes. By increasing the size of the acidicpore structure, such as that found in H-Y zeolite, one can realize acatalyst that favors the formation of long, branched-chain and cyclicalkanes and alkenes with less than 10% aromatics. Finally, with the useof zeolite such as H-beta, one obtains hydrocarbon products showing onlyC₁-C₃ alkanes and alkenes. This novel concept of the present inventionof shape and/or size selectivity can be extended to other porous, acidicsolids to develop the desired hydrocarbon products to includedistillates such as jet, diesel, and kerosene.

Additional metals and non-metals are often added to a catalystformulation to improve the properties and performance of the catalyst.In the case of the alcohol-forming metal component, alkali and alkaliearths are added in low loadings to the metal to decrease the carbondioxide forming reactions, such as the water gas shift reaction. ZhenyuLiu, Xianguo Li, Michael R. Close, Edwin L. Kugler, Jeffrey L. Petersen,and Dady B. Dadyburjor, “Screening of Alkali-PromotedVapor-Phase-Synthesized Molybdenum Sulfide Catalysts for the Productionof Alcohols from Synthesis Gas”, Ind. Eng. Chem. Res., 1997, 36 (8), pp.3085-3093. Also, changing the metal oxide to the metal sulfide has beenshown to decrease the conversion of carbon monoxide to carbon dioxide.Kegong Fang, Debao Li, Minggui Lin, Minglin Xiang, Wei Wei and YuhanSun, “A short review of heterogeneous catalytic process for mixedalcohols synthesis via syngas”, Catalysis Today, Volume 147, Issue 2, 30Sep. 2009, pp. 133-138. Accordingly, the metal syngas conversioncomponent will be modified with the addition of alkali and alkalineearth oxides together with sulfiding of the metal to form the metalsulfide.

The catalytic agent to accomplish the conversion of the presentinvention in a single catalyst bed is comprised of two functions whichare inculcated into the catalyst particles: a CO conversion elementwhich reduces the carbon monoxide into organic acids, esters, aldehydes,ketones, ethers, and alcohols; and an oxygenatedehydration/decarboxylation conversion element which reduces this listof oxygenates (organic acids, esters, aldehydes, ketones, ethers, andalcohols) into hydrocarbons, carbon dioxide, and water.

The oxygenate dehydration/decarboxylation conversion element may bechosen from a family of high surface area, acidic solids such as thecrystalline, alumino-silicates (H⁺-ZSM-5, Y-faujasite, H-beta,X-faujasite, mordenite, etc.), the mesoporous solids derived from thesol/gel/template process (MCM-41, etc.), or the amorphous silicaalumina, and heteropolyacids, etc. The choice of acidic solid willdetermine the types of hydrocarbons that will be made by this process.For example, when the acidic solid is H⁺-ZSM-5, a highly acidic,medium-sized pore (˜0.56 nm) zeolite, then the hydrocarbon liquids willbe characterized by a composition that is >90 wt % aromatics with theremainder being paraffins/iso-paraffins. When the acidic solid isY-faujasite, a large-pore zeolite, ˜0.9 nm, of intermediate acidity, theliquid products are >90 wt % cycloparaffins and iso-paraffins with theremainder being aromatic compounds. Finally, for an acidic solid such asH-beta, no liquid hydrocarbons are produced and the light hydrocarbongases are characterized by large amounts of ethylene and propylene. Themetals mentioned above may be deposited onto these high surface areasupports using the technique known as incipient wetness technique oralso known as the “pore filling” technique.

The CO conversion element which reduces the carbon monoxide into theoxygenates can be chosen from a list of transition metals to includemolybdenum, rhodium, rhenium, and combinations of these metals/metaloxides. Some of these transition metals may be converted to the sulfidestate, MoS₂, to enhance the selectivity to the desired hydrocarbons.Other catalyst cluster materials which may be added to promote thedesired reactions include at least one metal modifier member of theelements of Groups IA and IIA of the Periodic Table, as referenced by S.R. Radel and M. H. Navidi, in Chemistry, West Publishing Company, NewYork, 1990, and mixtures of these elements, including but not limited tolithium, sodium, potassium, rubidium, cesium, beryllium, magnesium,calcium, strontium, and barium.

The present invention discloses novel catalysts and a novel process andsystem utilizing these catalysts for converting low H₂/CO molar ratiosynthesis gas to hydrocarbon mixtures composed of high quality gasoline,low molecular weight gaseous olefins, and/or benzene/naphthalene-derivedaromatic compounds. The invention uses catalysts comprising molybdenum(Mo) or rhenium (Re) as the main active components for the reaction. Thecatalysts use a zeolite (HZSM-5, Y, Mordenite, MCM-22, MCM-41,H-Y-faujasite, H-beta, and the like) as the supporting material. Theactive phase of the catalysts is composed of carburized/reducedMo-species (Re) or a non-zeolite, such as silica-alumina,heteropolyacid, while the reaction proceeds mainly inside cages of thezeolite support, which thereby effectively inhibits the formation ofheavier linear-chain hydrocarbons (>C₇). Finally, the catalysts producealcohols (methanol, ethanol, and propanol) as the primary intermediateproducts for hydrocarbon formation which results from the dehydration ofthese alcohols. The process of the present invention removes one or morereactors in the process of producing high quality gasoline hydrocarbonproducts and produces such products from syngas in only one step orreactor.

The novel catalysts are suitable for synthesis using lower H₂/CO molarratio syngas and comprise carburized/reduced Mo-species (Re), a zeolite,and at least one alkali metal as the promoter, where the metal isselected from elements of Groups IA and IIA of the Periodic Chart andcombinations or mixtures thereof. In one formulation or embodiment,these catalysts produce liquid hydrocarbons enriched with lower branchedalkanes and alkyl-substituted aromatics. The aromatics content of thehydrocarbon liquids can be greatly reduced when the H-ZSM-5 is replacedwith H-Y-faujasite to make a liquid product that is mainly iso- andcyclo-paraffins. The catalysts and process of the present inventionproduce mainly branched alkanes and alkyl-substituted aromatics as highquality gasoline components, which differs from traditional Fe- andCo-based Fischer-Tropsch synthesis and catalysts that produce mainlylinear-chain hydrocarbons and that requires further processing viaadditional steps or reactors.

The process and system of the present invention converts syngas intohigh quality gasoline components (more than 90% branched/cyclicproducts) in one reactor. The conversion occurs over an alcohol-formingcatalyst found in the same matrix as a gasoline-forming catalyst,whereby the alcohol-forming catalyst creates or produces higher alcoholsfrom syngas. One embodiment of the present invention is a processwhereby syngas is converted into high quality gasoline hydrocarboncomponents (more than 90% branched/cyclic paraffin products) over amolybdenum-zeolite catalyst in high pressure hydrogen. The molybdenumallows the conversion of olefins/lower alcohols (that are initiallyformed in the catalytic process) into higher alcohols (C₂, C₃, C₄). Thezeolite allows the conversion of syngas into hydrocarbons; alcohols intoliquid hydrocarbons; higher alcohols into aromatic liquid hydrocarbons;and long, linear hydrocarbons into branched/cyclic hydrocarbons. Anotherembodiment of the present invention is a process whereby syngas inconverted into high quality gasoline hydrocarbon components (more than90% branched/cyclic paraffinic products) over a rhenium-zeolite catalystin high pressure hydrogen. In yet another embodiment, the metal functioncan be placed on H-beta to produce a catalyst which converts thesynthesis gas mainly to a gas mixture containing low molecular olefins,such as ethylene and propylene.

FIG. 1 illustrates graphically the overall process of the presentinvention. Solid biomass, coal, and/or heavier oil is gasified to formsyngas. The syngas is exposed to a zeolite-encaged molybdenum-based orrhenium-based catalyst. The product that results is a combination of gasand liquid. The liquid products are separated out using a gas-liquidseparation unit and comprise the high quality end product. The gasproducts are recycled back for reprocessing.

The invention is further clarified by the following examples, which areintended to be purely illustrative of the use of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from a consideration of this specification or practice of theinvention as disclosed herein. All percentages are on a mole percentbasis and selectivities are on a carbon atom percent basis, unless notedotherwise.

Example 1 Catalyst Synthesis

Mo/zeolite catalysts were prepared by incipient wetness impregnation of(NH₄)₆MO₇O₂₄4H₂O (Fisher Scientific) aqueous solution with the ammoniumform of either: 1) ZSM-5 (SiO₂/Al₂O₃=23, 50, 80, and 280), 2) zeolite Y(SiO₂/Al₂O₃=80) or zeolite β (SiO₂/Al₂O₃=25) obtained from ZeolystInternational. The designated Mo loading amount was 5 wt. % or 10 wt. %.The samples were finally calcined in air at 773 K for 3 h and pelletizedinto 0.25-0.5 mm particles for activity tests.

One detailed description of the preparation is as follows. Ninety-five(95) grams of H-ZSM-5 (SiO₂/Al₂O₃=50) were treated with an aqueoussolution of 9.5 g of (NH₄)₆Mo₇O₂₄.4H₂O dissolved in 47.7 grams ofdistilled water. The amount of water used in this incipient wetnesspreparation was just sufficient to fill the pores of the H-ZSM-5. Theresulting solid was dried at 110° C. for 18 hours before it was calcinedfor 3 h at 500° C. Other catalysts were prepared using H-ZMS-5 havingSiO₂/Al₂O₃=23, 80, and 280 and the protocol listed in this example.

Example 2 Catalyst Synthesis

Ninety-five (95) grams of Y-faujasite (SiO₂/Al₂O₃=80) were treated withan aqueous solution of 9.5 g of (NH₄)₆MO₇O₂₄.4H₂O dissolved in 95 gramsof distilled water. The amount of water used in this incipient wetnesspreparation was just sufficient to fill the pores of the Y-faujasite.The resulting solid was dried at 110° C. for 18 hours before it wascalcined for 3 h at 500° C.

Example 3 Catalyst Synthesis

Ninety-five (95) grams of H-beta zeolite (SiO₂/Al₂O₃=25) were treatedwith an aqueous solution of 9.5 g of (NH₄)₆MO₇O₂₄.4H₂O dissolved in 75grams of distilled water. The amount of water used in this incipientwetness preparation was just sufficient to fill the pores of theY-faujasite. The resulting solid was dried at 110° C. for 18 hoursbefore it was calcined for 3 h at 500° C.

Example 4 Catalyst Testing

The synthesis gas conversion to hydrocarbon liquids reaction wasperformed using a continuous flow, fixed-bed BTRS-Jr Laboratory ReactorSystems from Autoclave Engineers. Before the reaction, the catalyst (1.0g) was pretreated in syngas (H₂/CO=1.0) flow at 673 K for 1 h. The gashourly space velocity (GHSV) was 3000 h⁻¹. Liquid products werecollected using a condenser kept at 271 K and the pressure was 500 psigand 1000 psig, respectively, and the effluent gas from the condenser wasanalyzed with an on-line gas chromatograph (GC, HP 6980) equipped withthermal conductive detector (TCD) and flame ionization detector (FID). Apacked Molecular Sieve 5A column and a HP-1 capillary column wereemployed for separation of inorganic gases and light hydrocarbons.Liquid products, collected from the condenser, were separated into anoil phase and a water phase, and analyzed with GC-mass spectrometer(Agilent) equipped with DB-Wax capillary column for oxygenated compoundsand HP-5 ms capillary column for hydrocarbons. Six (6) % N₂ was addedinto the syngas as internal standard for CO conversion calculation.Selectivity of lower hydrocarbons was estimated on carbon basis based onFID signal. The catalyst activity and selectivity were calculatedaccording to Equations (1) and (2), respectively, (below) where F^(o)and F are the flow rates of the syngas and effluent gas after thereaction, respectively; C^(o) _(i) and C_(i) are the concentrations ofcomponent i in the syngas and effluent gas, respectively; and n is thecarbon number in a product i molecule:

Conversion of CO (%)=[F ^(o) C ^(o) _(CO) −FC _(CO) ]/F ^(o) C ^(o)_(CO)=100×[C ^(o) _(CO) −C ⁰ _(N2)(C _(CO) /C _(N2))]/C ^(o) _(CO)  (1)

Selectivity of product I (%)=nFC _(i) /[F ^(o) C ^(o) _(CO) −FC_(CO)]=100×nC ^(o) _(N2) C _(i) /[C _(N2) C ^(o) _(CO) −C ^(o) _(N2) C_(CO)]  (2)

In the first reaction example (4), the GHSV was 3,000 h⁻¹, the reactiontemperature was 573 K, the pressure was 1000 psi, and the catalyst wasthe 5 wt % Mo/HZSM-5 zeolite showing a SiO₂/Al₂O₃=23. The conversion andselectivity results are shown in Table 1.

Example 5 Catalyst Testing

In example (5), the GHSV was 3,000 h⁻¹, the reaction temperature was 623K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5zeolite showing a SiO₂/Al₂O₃=23. The conversion and selectivity resultsare shown in Table 1.

Example 6 Catalyst Testing

In example (6), the GHSV was 3,000 h⁻¹, the reaction temperature was 573K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/HZSM-5zeolite showing a SiO₂/Al₂O₃=50. The conversion and selectivity resultsare shown in Table 1. The liquid product distribution is shown in Table2.

Example 7 Catalyst Testing

In example (7), the GHSV was 3,000 h⁻¹, the reaction temperature was 623K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5zeolite showing a SiO₂/Al₂O₃=50. The conversion and selectivity resultsare shown in Table 1. The liquid product distribution is shown in Table2.

Example 8 Catalyst Testing

In example (8), the GHSV was 3,000 h⁻¹, the reaction temperature was 573K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/HZSM-5zeolite showing a SiO₂/Al₂O₃=80. The conversion and selectivity resultsare shown in Table 1. The liquid product distribution is shown in Table2.

Example 9 Catalyst Testing

In example (9), the GHSV was 3,000 h⁻¹, the reaction temperature was 623K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5zeolite showing a SiO₂/Al₂O₃=80. The conversion and selectivity resultsare shown in Table 1. The liquid product distribution is shown in Table2.

Example 10 Catalyst Testing

In example (10), the GHSV was 3,000 h⁻¹, the reaction temperature was573 K, the pressure was 1000 psi, and the catalyst was the 5 wt %Mo/HZSM-5 zeolite showing a SiO₂/Al₂O₃=280. The conversion andselectivity results are shown in Table 1.

Example 11 Catalyst Testing

In example (11), the GHSV was 3,000 the reaction temperature was 623 K,the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5zeolite showing a SiO₂/Al₂O₃=280. The conversion and selectivity resultsare shown in Table 1.

Example 12 Catalyst Testing

In example (12), the GHSV was 3,000 the reaction temperature was 573 K,the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/H-Yzeolite showing a SiO₂/Al₂O₃=80. The conversion and selectivity resultsare shown in Table 1. The liquid product distribution is shown in Table2.

Example 13 Catalyst Testing

In example (13), the GHSV was 3,000 h⁻¹, the reaction temperature was573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/H-βzeolite showing a SiO₂/Al₂O₃=25. The conversion and selectivity resultsare shown in Table 1.

Example 14 Catalyst Testing

In example (14), the GHSV was 3,000 the reaction temperature was 623 K,the pressure was 500 psi, and the catalyst was the 5 wt % Mo/H-β zeoliteshowing a SiO₂/Al₂O₃=25. The conversion and selectivity results areshown in Table 1.

TABLE 1 Examples Showing Reaction Results Example SiO₂/ Temperature,Pressure, Number Catalyst Al₂O₃ K psi 4 5% Mo/HZSM-5 23 573 1000 5 5%Mo/HZSM-5 23 623 500 6 5% Mo/HZSM-5 50 573 1000 7 5% Mo/HZSM-5 50 623500 8 5% Mo/HZSM-5 80 573 1000 9 5% Mo/HZSM-5 80 623 500 10 5% Mo/HZSM-5280 573 1000 11 5% Mo/HZSM-5 280 623 500 12 5% Mo/H-Y 80 573 1000 13 5%Mo/H-β 25 573 1000 14 5% Mo/H-β 25 623 500 Example CO ProductSelectivity, % Number Conversion % CO₂ C₁-C₃ C₄ ⁺-Hydrocarbons 4 10.558.6 15.5 2.9 5 47.5 54 47.1 — 6 15.2 49.6 24.5 25.8 7 31.8 51.7 35.213.0 8 32.4 62.3 26.7 11.0 9 51.2 57.6 41.8 0.6 10 20.6 64.2 25.5 10.311 44.6 61.7 36.5 1.8 12 13.9 38.6 30.4 31.0 13 13.5 61.0 39.0 — 14 39.161.3 38.7 —

TABLE 2 Liquid Product Distribution SiO₂/ Example Catalyst Al₂O₃Temperature Pressure, psi 6 5% Mo/HZSM-5 50 573 1000 7 5% Mo/HZSM-5 50623 500 8 5% Mo/HZSM-5 80 573 1000 9 5% Mo/HZSM-5 80 623 500 12 5%Mo/H-Y 80 573 1000 Product Distribution % Branched Linear Linear % &Cyclized Example Alkanes Alkenes Aromatics Alkanes 6 15 5 30 50 7 12 545 38 8 5 0 65 30 9 5 2 80 13 12 35 5 10 50

This disclosure has for the first time described and fully characterizeda novel process and system in which syngas is converted into highquality gasoline components, aromatic compounds, and lower molecularolefins in one reactor. The invention utilizes a novelmolybdenum-zeolite catalyst in high pressure hydrogen for conversion anda novel rhenium-zeolite catalyst in place of the molybdenum-zeolitecatalyst in high pressure hydrogen for conversion.

The above detailed description is presented to enable any person skilledin the art to make and use the invention. Specific details have beendisclosed to provide a comprehensive understanding of the presentinvention and are used for explanation of the information provided.These specific details, however, are not required to practice theinvention, as is apparent to one skilled in the art. Descriptions ofspecific applications, analyses, and calculations are meant to serveonly as representative examples. Various suitable changes,modifications, combinations, and equivalents to the preferredembodiments may be readily apparent to one skilled in the art and thegeneral principles defined herein may be applicable to other embodimentsand applications while still remaining within the spirit and scope ofthe invention. The claims and specification should not be construed tounduly narrow the complete scope of protection to which the presentinvention is entitled. It should also be understood that the figures arepresented for example purposes only. There is no intention for thepresent invention to be limited to the embodiments shown and theinvention is to be accorded the widest possible scope consistent withthe principles and features disclosed herein.

1. A process for the production of hydrocarbon fuel products fromsynthesis gas comprising a single reactor system and a steam reformer,wherein chemical reactions in the single reactor system occur over analcohol-forming catalyst found in the same matrix as a gasoline-formingcatalyst and wherein the alcohol-forming catalyst produces high qualityalcohols from the synthesis gas.
 2. The process of claim 1, wherein thesynthesis gas is contacted in a Fischer-Tropsch reaction with thealcohol-forming catalyst in high pressure hydrogen.
 3. The process ofclaim 2, wherein the catalyst is a zeolite-encaged, molybdenum-basedcatalyst active for deoxy-aromatization of alcohols and synthesis gas tomixed alcohols, isomerization of alkanes, and aromatization.
 4. Theprocess of claim 3, wherein the catalyst is a cluster comprising amolybdenum oxide represented by MoC_(x)O_(y) encaged in a zeolite andwherein the cluster comprises the active phase.
 5. The process of claim4, wherein the cluster comprises a molybdenum sulfide.
 6. The process ofclaim 4, wherein the cluster further comprises at least one metalmodifier selected from the group consisting of the elements of Groups 1Aand 2A of the Periodic Table and mixtures of the aforementionedelements.
 7. The process of claim 3, wherein the zeolite comprises asupport.
 8. The process of claim 7, wherein the zeolite comprises one ormore members selected from the group consisting of the zeolite-basedheterogeneous catalyst HZSM-5, Y, Mordenite, MCM-22, MCM-41,H-Y-faujasite, and H-beta zeolites.
 9. The process of claim 2, whereinthe catalyst is a zeolite-encaged, rhenium-based catalyst active fordeoxy-aromatization of alcohols and synthesis gas to mixed alcohols,isomerization of alkanes, and aromatization.
 10. The process of claim 9,wherein the catalyst is a cluster comprising a rhenium oxide representedby ReC_(x)O_(y) encaged in a zeolite and wherein the cluster comprisesthe active phase.
 11. The process of claim 10, wherein the clustercomprises a rhenium sulfide.
 12. The process of claim 10, wherein thecluster further comprises at least one metal modifier selected from thegroup consisting of the elements of Groups 1A and 2A of the PeriodicTable and mixtures of the aforementioned elements.
 13. The process ofclaim 9, wherein the zeolite comprises a support.
 14. The process ofclaim 13, wherein the zeolite comprises one or more members selectedfrom the group consisting of the zeolite-based heterogeneous catalystHZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, and H-betazeolites.
 15. The process of claim 1, wherein the hydrocarbon fuelproducts comprise liquid hydrocarbons and gas hydrocarbons and whereinthe products are separated in a separation unit.
 16. The process ofclaim 15, wherein the liquid hydrocarbons comprise branched alkanes andalkyl-substituted aromatics.
 17. The process of claim 15, wherein thegas hydrocarbons are fed to and processed through the steam reformer andreturned to the single reactor system.
 18. A catalyst for the productionof hydrocarbon fuel products from synthesis gas comprising a molybdenumcatalyst encaged in a zeolite support comprising one or more membersselected from the group consisting of HZSM-5, Y, Mordenite, MCM-22,MCM-41, H-Y-faujasite, and H-beta zeolites.
 19. The catalyst of claim18, further comprising at least one alkali metal as a promoter forminimizing carbon dioxide products in the production of hydrocarbon fuelproducts, wherein the alkali metal is selected from the group consistingof the elements of Groups 1A and 2A of the Periodic Table and mixturesthereof.
 20. The catalyst of claim 18, wherein the molybdenum catalystis chosen from the group consisting of molybdenum oxide and molybdenumsulfide.
 21. The catalyst of claim 19, wherein the size and shape of thecatalyst encaged in the zeolite support selected determines the types ofhydrocarbon fuel products that are produced.
 22. A catalyst for theproduction of hydrocarbon fuel products from synthesis gas comprising arhenium catalyst encaged in a zeolite support comprising one or moremembers selected from the group consisting of HZSM-5, Y, Mordenite,MCM-22, MCM-41, H-Y-faujasite, and H-beta zeolites.
 23. The catalyst ofclaim 22, further comprising at least one alkali metal as a promoter forminimizing carbon dioxide products in the production of hydrocarbon fuelproducts, wherein the alkali metal is selected from the group consistingof the elements of Groups 1A and 2A of the Periodic Table and mixturesthereof.
 24. The catalyst of claim 22, wherein the rhenium catalyst ischosen from the group consisting of rhenium oxide and rhenium sulfide.25. The catalyst of claim 23, wherein the size and shape of the catalystencaged in the zeolite support selected determines the types ofhydrocarbon fuel products that are produced.
 26. A catalyst system forproducing a hydrocarbon liquid having an aromatics content of about 90%or greater, wherein the system comprises a metal on an HZSM-5 zeolite.27. A catalyst system for producing a hydrocarbon liquid having acyclo-paraffin and iso-paraffin content of about 90% or greater, whereinthe system comprises a metal on an H-Y-faujasite zeolite.
 28. A catalystsystem for producing an ethylene-rich and propylene-rich hydrocarbon gasand producing no hydrocarbon liquid, wherein the system comprises ametal on an H-beta zeolite.
 29. The process of claim 1, wherein thechemical reactions produce a hydrocarbon liquid having an aromaticscontent of about 90% or greater and wherein the alcohol-forming catalystcomprises a metal on an HZSM-5 zeolite.
 30. The process of claim 1,wherein the chemical reactions produce a hydrocarbon liquid having acyclo-paraffin and iso-paraffin content of about 90% or greater andwherein the alcohol-forming catalyst comprises a metal on anH-Y-faujasite zeolite.
 31. The process of claim 1, wherein the chemicalreactions produce an ethylene-rich and propylene-rich hydrocarbon gasand produce no hydrocarbon liquid and wherein the alcohol-formingcatalyst comprises a metal on an H-beta zeolite.